Recovery of spent selenium



June 27, 1933.

l C. C. TOWNE ET AL RECOVERY OF SPENT SELENIUM Filed May 18, 1932 @NNN NK ma MCR Y m M c. .N R www0 o L N TQ e W Cf E H Y n B m Patented June 27, l1933 UNITED STATES PATENT. ori-ica CHARLES C. TOWNE, 0I POUGHIEEPSIE, HERBERT C. BECKER, 0F BEACGN, NIW.-

'YOBK ASSIGNOBS OF v:DELAYTABE application mea lay 18,'

i' spent selenium from the products of conversionobtained in the pyrolysis of hydrocarbons in the presence of selenium. The object of the inventionis to recover the spent selenium in a. form suitable for reuse.

In accordance 'with the invention, the conversion products, such as naphtha and uncondensable gases, resulting from the pyrolysis operation, are contacte with an aqueous alkaline solution, whereby the volatile spent selenium is extracted as alkali soluble compounds by the solution and then the extractedcompounds are oxidized to precipitate free selenium. A

In the treatment of hydrocarbon oils andgases to effect conversion thereof into products suitable for the manufacture of motor fuel it is often advantageous tocarry out the operations in the presence of selenium, as disclosed in the copending applications of Charles C. Towne: Serial No. 591,306, filed undesirable because o tamed selenlum.

February 6, 1932 and Serial No. 607,755 led April 27, 1932; and a copending-ap lication of Charles C. Towne and LeRoy Story, Serial No. 607,7 54, filed April 27, 1932. Such a treatment usually causes a substantial amount of reaction between the selenium and hydrocarbons or hydrogen formed in the process, with the formation of compounds of selenium, such as hydrogen selenide, alkyl selenides and alkyl hydroselenides. These compounds are mostly volatile substances .which vaporize along with the conversion products and escape in the uncondensable gases .or partially dissolve lin the distillate. The loss of these com ounds is economically i) the valueofthe con- By means of our invention it is possible substantially completely to recover the spentv selenium in the volatile conversion products in a form suitable for reuse as a catalyst or conversion agent by a sim le and inexpensive method. By our process the conversion products, preferably' the lighter. portion thereof,

" Vsuch as Ythe naphtha, uncondensable gases, or both, are -contacted vor scrubbed, in a counterflow apparatus or otherwise, with an alkaline solution adapted to extract selenium from` RECOVERY 0F SPENT SELENIUI 1932. Serial No. 612,120.'

the hydrocarbons. The selenium is extracted by the alkali in the form of a salt or a selenide which is ordinarily soluble in the alkaline solution. The solution containing they selenium is-then subjected to anoxidation reaction by agitating the solution with an oxidizing agent, such as hydrogen'peroxide, oxygen, -air, or other oxy en-containing gas. The selenium compoundgs are oxidized and free selenium is precipitated in a granular form Aand may be filtered from the solution. The alkaline solution, after the separation of the precipitated selenium, may be used' over again for scrubbing additional hydrocarbons. The drawing is a flow chart showingv the application of the process to the recovery of selenium from the gases and the condensate -recovered from the final condenser in a conversion process. 1

An example will now be given of the operation of our process as applied to the recovery of selenium from the cracked products obtained in the reforming of naphtha, wherein a straight run naphtha of about 40 octane number was reformed into about 78% of a motor fuel having about the same boiling point but 78 octane number, 2% of and the remainder of uncondensa le gases. The4 gases from the operation were washed with about lbarrel of 5% soda ash per thou sand cubic feet and the naphtha was washed with about 1 gallon per Abarrel of 10% caustic solution. The soda ash and caustic solutions were then blown with air at' approximately 150 F. until the selenium was substantially entirely precipitated 'as indicatediby the comlymers,

in the reforming operation. In this wayh substantially allgof the seleniumconsumed continuously.

in the conversion operation may be recovered ma is the most satisfactory scrubbing agent in normaloperation for scrubbing either gaseous or liquidproducts because of the relu-- tively high solubility of tlie alkali selenides therein. When usin caustic soda, it is ott/env advantageous to com ine a Water wash with tbe alkaline scrubbing operation in order to f avoid precipitation of crystals which may cause plugging oi lines or other pieces of tbe equipment. 'lhe strength of tbe alkaline solutions may range from .about .2-l5%, by Wei bt, or biglier. Also tbe temperature for oni izinn may range from roorn temperature to near tbe boiling points oi the solutions.

lin cases Where it is desired to completely separete tbe selenium from the alkaline solos tions, tbe idltrate, alter separation oi tbe inajor portion of the selenium as described above, may be acidied, lor example, with suitable acid, suoli as hydrochloric acid, and

` sulfur dioxide bubbled therethrough or seine other reducing agent added to reduce any selenious acid or other oxidation products. tlrdinarily, tbe complete separation oni tbe selenium from tbe alkaline solutions is not essential to tbe operation oil tbe process unn less excessive amounts ofi unrecovered seletio' niuniv compounds accumulate in tbe solutions. lns'nd ol? naslnnp,7 tbegescs naplitba separately, they may botti be vrasl'ned to-n vgetlier ivitl tbe saine solution; to

tbe eticiency and simplicity oli tbe op-` eration, tbe scrubbing may be performed in tbe condensing step or prior tliereto, .ior en ample, in tlie deplilegniator, or a separate scrubber niuy be installed at any suitable place 'abend Voli tbe linal condenser.

liltbougb 'We bave described a process in relotion `to certain theoretical sliould be understood that We do not intend tov linut ourselves to 'tbe correstness tliereoii.

bviously, inany iuodications and varian tions oi. tbe invention., as bereinbetore set forth, inay be inode Witliout departing1 irons tbe epiritand scope there-oli, and therefore onlysucb limitations should be impose are indicated in tbe appended cloiins.

reactions, it Y narrates We claim: l

l. The method for the recovery of selenium from hydrocarbons after subjection to a conversion operation in the presence of selenium which comprises extracting the selenium compounds from the cracked products by means oil an alkali and then precipitating the selenium from the alkali by means oi an oxidizing agent.

2. 'llie metli'od for the recovery of spent selenium in a pyrolytic cracking process'in l which selenium is used as a catal st, :which comprises scrubbing tbe volatilize products from the cracking operation with an aqueous alkali to extract the selenium compounds therein, then subjecting tbe alkali extract to an oxidation operation to precipitate the selennun.. v

3. ln tbe conversion oi hydrocarbons vvlierein selenium is used as a catalyst and the spent selenium is normally lost as volatile compounds in tbe lower boiling roducts, suoli es tbe napbtlia and uncondensa le gases, tbe improvement vvliicli corn rises recovering tbe selenium by "scrubbing t e lovver'boiling il@ products with au aqueous alkaline solution to extract tbe selenium from said roducts in tbe torni ol a salt, and tlien oxidizing tbe salt to liberate tbe selenium.

i. lllie nietbod according to claim 3 in vvbicb tbe concentration of tbe allrali in tbe solution is about 2i5% by weight.

5. lln tbe recovery oit spent selenium frein a hydrocarbon conversion process vzrlierein tbe liti selenium is used as catalyst for tbe conu "lill version ont tbe bydrocarbons, tbe steps oi sublooting a portion of `tbc vaoorized converted productscontaining voluti e seleniuni compounds to a serubbiru?1 operation ivitb en aqueous allali to entract te selenium '5% as an alkali selenide soluble in 'tbe aqueous solution, tlien contacting nir. vvitb tbe solution to precipitate tbe selenium and recovering tbe precipitated selenium. l

li.. lloc rnetbod accordine to claim 5 in f ll@ vvliicli tbe temperature oi tire aqueous solution oit alkali selenide when contacted vvitli air isebout loll" lil-200 l?.

ln Witness vvliereoii vve lieve utilised our signatures. M5

@MUSS C. TWNE. HERBERT (C. lillllmld.r 

